Crystalline modification of a manganese complex

ABSTRACT

This invention relates to a novel crystal form of the 1:1 manganese (III) complex of N,N′,N″tris[salicylideneaminoethyl]amine, a process for its preparation and the use thereof.

This application is the National Stage of International ApplicationPCT/EP04/000359, filed on Jan. 19, 2004.

This invention relates to a novel polymorph crystal form of the 1:1manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine, aprocess for its preparation and the use thereof.

N,N′,N″-tris[salicylideneaminoethyl]amine (saltren)

the 1:1 manganese(III) complex (Mn(III)saltren) thereof

its production as well as its use as peroxygen catalyst are known forexample from WO0105925 (Examples 1 and 13), WO0109276 (Example 53) andWO02059245 (Example 15). The Mn(III) saltren compound has been known andproducible as an amorph modification only.

The ability of a substance to exist in more than one crystal form isdefined as polymorphism and these different crystal forms are named“polymorph modifications” or “polymorphs”. In general, polymorphism isaffected by the ability of a molecule of a substance to change itsconformation or to form different intermolecular or intra-molecularinteractions, particularly hydrogen bonds, which is reflected indifferent atom arrangements in the crystal lattices of differentpolymorphs.

The different polymorphs of a substance possess different energies ofthe crystal lattice and, thus, in solid state they show differentphysical properties such as form, density, melting point, colour,stability, dissolution rate, milling facility, granulation, compactingetc.

Surprisingly a new crystal modification of the 1:1 manganese (III)complex of N,N′,N″-tris[salicylideneaminoethyl]amine

which is characterized by a peak at a d-spacing of about 6.87 Å in itspowder X-ray diffraction pattern, has been found.

Specifically, the new crystal modification of the 1:1 manganese (III)complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) ischaracterized by peaks with d-spacings of about 6.87 and 12.69 Å in itspowder X-ray diffraction pattern.

More specifically, the new crystal modification of the 1:1 manganese(III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound(2)) is characterized by peaks with d-spacings of about 3.51, 3.65,4.20, 4.63, 4.95, 5.30, 6.38, 6.87, 7.50, 10.57 and 12.69 Å in itspowder X-ray diffraction pattern.

Very specifically, the new crystal modification of the 1:1 manganese(III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound(2)) is characterized by peaks with d-spacings of about 2.22, 2.48,2.94, 3.14, 3.51, 3.65, 3.76, 3.94, 4.20, 4.63, 4.95, 5.30, 5.82, 6.19,6.38, 6.87, 7.50, 8.59, 10.57 and 12.69 Å in its powder X-raydiffraction pattern.

The powder sample of the new crystal modification of Mn(III)saltren(compound (2)) has been analysed by a STOE-powder-diffractometer at roomtemperature (25° C.) under Cu X-ray [λ(CuKα)=1.540598 Å].

Table 1 shows the characteristic spacing between the lattice planesdesignated by d and expressed in Angstrom units [Å] and theircorresponding characteristic relative intensity (weak, medium orstrong).

TABLE 1 d(Å) Intensity 12.69 strong 10.57 medium 8.59 weak 7.50 medium6.87 strong 6.38 medium 6.19 weak 5.82 weak 5.30 medium 4.95 medium 4.63medium 4.20 medium 3.94 weak 3.76 weak 3.65 medium 3.51 medium 3.14 weak2.94 weak 2.48 weak 2.22 weak

FIG. 1. shows the powder X-ray diffraction pattern of Mn(III)saltren(compound (2)), obtained from Example 1. The values are given in 2θ.

FIG. 2. shows the powder X-ray diffraction pattern of Mn(III)saltren(compound (2)), obtained from Example 2. The values are given in 2θ.

The following formula shows the relation between d and 2θ:

${d(Å)} = \frac{1.54060\mspace{20mu} Å}{2\;\sin\;\left( {2{\theta/2}} \right)}$

In addition, by recording a single crystal of the new crystalmodification of Mn(III)saltren (compound (2)) in a STOE Stadi4-circle-diffractometer D045 under Mo X-rays [λ(MoK_(α))=0.71073 Å] at293 K, there were obtained the basic crystallographic data for a singlecell.

The size of the crystal has been 0.5 mm×0.35 mm×0.2 mm.

The basic crystallographic data (diffraction on single crystal) for thenew crystal modification of Mn(III)saltren (compound (2)) are shown inTable 2.

TABLE 2 Crystal system Monoclinic Space group P 2₁/n a[Å] 7.906 b[Å]25.609 c[Å] 11.736 α[°] 90 β[°] 96.55 γ[°] 90 V[Å³] 2360.6 Structureunit per cell (Z) 4 Absorption coefficient μ [mm⁻¹] 0.597 F(000) 1064

In comparison to the amorph modification, the new crystal modificationof Mn(III)saltren (compound (2)) has improved properties.

The new crystal modification posses for example improved formulationproperties in comparison to the amorph modification. Further, the newcrystal modification has an improved filterability.

The new crystal modification of Mn(III)saltren (compound (2)) can beused for improving the action of peroxides, for example in the treatmentof textile material, without at the same time causing any appreciabledamage to fibres and dyeings.

Peroxide-containing bleaching agents have been used in washing andcleaning processes for some time. They have an excellent action at aliquor temperature of 90° C. and above, but their performance noticeablydecreases with lower temperatures. It is known that various transitionmetal ions, added in the form of suitable salts, or coordinationcompounds containing such cations catalyse the decomposition of H₂O₂. Inthat way it is possible to increase the bleaching action of H₂O₂, or ofprecursors that release H₂O₂, or of other peroxo compounds, thebleaching action of which is unsatisfactory at lower temperatures.Particularly significant for practical purposes are those combinationsof transition metal ions and ligands the peroxide activation of which ismanifested in an increased tendency towards oxidation in respect ofsubstrates and not only in a catalase-like disproportionation. Thelatter activation, which tends rather to be undesirable in the presentcase, could impair the bleaching effects of H₂O₂ and its derivativeswhich are insufficient at low temperatures.

In respect of H₂O₂ activation having effective bleaching action,mononuclear and polynuclear variants of manganese complexes with variousligands, especially with 1,4,7-trimethyl-1,4,7-triazacyclononane andoptionally oxygen-containing bridge ligands, are currently regarded asbeing especially effective. Such catalysts have adequate stability underpractical conditions and, with Mn^(n+), contain an ecologicallyacceptable metal cation, but their use is unfortunately associated withconsiderable damage to dyes and fibres.

The invention accordingly relates to the use of the new polymorphcrystal modification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2))

as catalyst for oxidation reactions.

The new crystal modification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) is preferablyused together with peroxy compounds. Examples that may be mentioned inthat regard include the following uses:

-   a) the bleaching of spots or stains on textile material in the    context of a washing process or a (pre-)soaking process;-   b) the prevention of redeposition of migrating dyes during the    washing of textile material;-   c) the cleaning of hard surfaces, especially wall tiles or floor    tiles, more especially for removing mold stains;-   d) use in washing and cleaning solutions having an antibacterial    action;-   e) as pretreatment agents for bleaching textiles;-   f) as catalysts in selective oxidation reactions in the context of    organic synthesis;-   g) as catalyst for the waste water treatment.

A further use relates to the use of the new crystal modification of the1:1 manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) as catalyst for reactions with peroxy compounds forbleaching in the context of paper-making. This relates especially to thebleaching of pulp, which can be carried out in accordance with customaryprocesses. Also of interest is the use of the new crystal modificationof the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylidene-aminoethyl]amine (compound (2)) as catalystfor reactions with peroxy compounds for the bleaching of waste printedpaper.

Preference is given to the bleaching of spots or stains on textilematerial, the prevention of the redeposition of migrating dyes in thecontext of a washing process, or the cleaning of hard surfaces,especially wall or floor tiles.

It should be emphasised that the new crystal modification of the 1:1manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) does not cause any appreciable damage to fibres anddyeings, for example in the bleaching of textile material.

Processes for preventing the redeposition of migrating dyes in a washingliquor are usually carried out by adding to the washing liquor, whichcontains a peroxide-containing washing agent, the new crystalmodification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) in an amount offrom 0.1 to 200 mg, preferably from 0.2 to 75 mg, especially from 0.2 to30 mg, per liter of washing liquor. The new crystal modification of the1:1 manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) can be used together with other transition metalcomplexes. Such complexes are described for example in WO02088289,WO0105925, WO0109276, WO02059245, WO053574, EP902083 and EP955289.

The present invention relates also to a washing or cleaning agent,comprising

-   I) 0–50 wt-%, preferably 0–30 wt-%, A) of at least one anionic    surfactant and/or B) of at least one non-ionic surfactant,-   II) 0–70 wt-%, preferably 0–50 wt-%, C) of at least one builder    substance,-   III) 0–10 wt-%, preferably 0–5 wt-% D) of at least one    (poly)phosphonate and/or aminoalkylene-poly(alkylenephosphonate),-   IV) 1–99 wt-%, preferably 1–70 wt-%, E) of at least one peroxide    and/or of at least one peroxide-forming substance, and-   V) F) the new crystal modification of the 1:1 manganese (III)    complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound (2))    in an amount which, in the liquor, gives a concentration of 0.2–50    mg/liter of liquor, preferably 0.2–30 mg/liter of liquor, when from    0.2 to 20 g/liter of the washing, cleaning, disinfecting and    bleaching agent are added to the liquor.

Preferably, the present invention relates also to a disinfecting orbleaching agent, comprising

-   I) 0–20 wt-%, preferably 0–15 wt-%, A) of at least one anionic    surfactant and/or B) of at least one non-ionic surfactant,-   II) 0–60 wt-%, preferably 0–50 wt-%, C) of at least one builder    substance,-   III) 0–10 wt-%, preferably 0–5 wt-% D) of at least one    (poly)phosphonate and/or aminoalkylene-poly(alkylenephosphonate),-   IV) 1–99 wt-%, preferably 1–70 wt-%, E) of at least one peroxide    and/or of at least one peroxide-forming substance, and-   V) F) the new crystal modification of the 1:1 manganese (III)    complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound (2))    in an amount which, in the liquor, gives a concentration of 0.2–50    mg/liter of liquor, preferably 0.2–30 mg/liter of liquor, when from    0.2 to 20 g/liter of the washing, cleaning, disinfecting and    bleaching agent are added to the liquor.

The above percentages are in each case percentages by weight, based onthe total weight of the agent. The agents preferably contain from 0.005to 2 wt-% of the new crystal modification of the 1:1 manganese (III)complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound 2)),especially from 0.01 to 1 wt-% and preferably from 0.02 to 1 wt-%.

When the washing or cleaning agents according to the invention compriseat least one component A) and/or B), the amount thereof is preferably1–50 wt-%, especially 1–30 wt-%.

When the agents according to the invention comprise at least onecomponent C), the amount thereof is preferably 1–70 wt-%, especially1–50 wt-%. Special preference is given to an amount of from 5 to 50 wt-%and especially an amount of from 10 to 50 wt-%.

When the agents according to the invention comprise at least one(poly)phosphonate and/or aminoalkylene-poly(alkylenephosphonate), theamount thereof is preferably 0.1–3 wt-%, especially 1–3 wt-%. Thepreferred compounds are amino-trimethylene-phosphonic acid,diethylenetriamine penta(methylenephosphonic acid), ethylene diaminetetra(methylene phosphonic acid), as well as mixtures thereof and thesalts therefrom.

Corresponding washing, cleaning, disinfecting or bleaching processes areusually carried out by using an aqueous liquor comprising a peroxide andfrom 0.1 to 200 mg of the new crystal modification of the 1:1 manganese(III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound(2)) per liter of liquor. The liquor preferably contains from 0.2 to 30mg of the compound of formula (2) per liter of liquor.

The agents according to the invention can be, for example, aperoxide-containing complete washing agent or a separate bleachingadditive. A bleaching additive is used for removing coloured stains ontextiles in a separate liquor before the clothes are washed with ableach-free washing agent. A bleaching additive can also be used in aliquor together with a bleach-free washing agent.

It is also possible to prepare granules of the agent according to theinvention, for example, by first preparing an initial powder byspray-drying an aqueous suspension containing all the components listedabove except for components E) and F), and then adding the drycomponents E) and F) and mixing everything together. It is also possibleto add component F) to an aqueous suspension containing components A),B), C) and D), then to carry out spray-drying and then to mix componentE) with the dry mass.

It is also possible to start with an aqueous suspension that containscomponents A), C) and D), but none or only some of component B). Thesuspension is spray-dried, then component F) is mixed with component B)and added, and then component E) is mixed in in the dry state.

It is also possible to mix all the components together in the dry state.

The anionic surfactant A) can be, for example, a sulfate, sulfonate orcarboxylate surfactant or a mixture thereof. Preferred sulfates arethose having from 12 to 22 carbon atoms in the alkyl radical, optionallyin combination with alkyl ethoxysulfates in which the alkyl radical hasfrom 10 to 20 carbon atoms.

Preferred sulfonates are e.g. alkylbenzenesulfonates having from 9 to 15carbon atoms in the alkyl radical. The cation in the case of anionicsurfactants is preferably an alkali metal cation, especially sodium.

The anionic surfactant component may be, e.g., an alkylbenzenesulfonate,an alkylsulfate, an alkylethersulfate, an olefinsulfonate, analkanesulfonate, a fatty acid salt, an alkyl or alkenyl ethercarboxylate or an α-sulfofatty acid salt or an ester thereof. Preferredare alkylbenzenesulfonates having 10 to 20 carbon atoms in the alkylgroup, alkylsulfates having 8 to 18 carbon atoms, alkylethersulfateshaving 8 to 18 carbon atoms, and fatty acid salts being derived frompalm oil or tallow and having 8 to 18 carbon atoms. The average molarnumber of ethylene oxide added in the alkylethersulfate is preferably 1to 20, preferably 1 to 10. The salts are preferably derived from analkaline metal like sodium and potassium, especially sodium. Highlypreferred carboxylates are alkali metal sarcosinates of formulaR—CO(R₁)CH₂COOM₁ in which R is alkyl or alkenyl having 9–17 carbon atomsin the alkyl or alkenyl radical, R₁ is C₁–C₄ alkyl and M₁ is an alkalimetal, especially sodium.

The nonionic surfactant component may be, e.g., primary and secondaryalcohol ethoxylates, especially the C₈–C₂₀ aliphatic alcoholsethoxylated with an average of from 1 to 20 moles of ethylene oxide permole of alcohol, and more especially the C₁₀–C₁₅ primary and secondaryaliphatic alcohols ethoxylated with an average of from 1 to 10 moles ofethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactantsinclude alkylpolyglycosides, glycerol monoethers, and polyhydroxyamides(glucamide).

The total amount of anionic surfactant and nonionic surfactant in thewashing or cleaning agent is preferably 5–50 wt-%, preferably 5–40 wt-%and more preferably 5–30 wt-%. As to these surfactants it is preferredthat the lower limit is 10 wt-%.

The total amount of anionic surfactant and nonionic surfactant in thedisinfecting or bleaching agent is preferably 0–15 wt-%.

Preferred carboxylates are alkali metal sarcosinates of formulaR₂—CO—N(R₃)—CH₂COOM′¹ wherein R₂ is alkyl or alkenyl having from 8 to 18carbon atoms in the alkyl or alkenyl radical, R₃ is C₁–C₄alkyl and M′¹is an alkali metal.

The non-ionic surfactant B) can be, for example, a condensation productof from 3 to 8 mol of ethylene oxide with 1 mol of a primary alcoholhaving from 9 to 15 carbon atoms.

As builder substance C) there come into consideration, for example,alkali metal phosphates, especially tripolyphosphates, carbonates orhydrogen carbonates, especially their sodium salts, silicates,aluminosilicates, polycarboxylates, polycarboxylic acids, organicphosphonates, aminoalkylenepoly(alkylenephosphonates) or mixtures ofthose compounds.

Especially suitable silicates are sodium salts of crystalline layeredsilicates of the formula NaHSi_(t)O_(2t+1).pH₂O orNa₂Si_(t)O_(2t+1).pH₂O wherein t is a number from 1.9 to 4 and p is anumber from 0 to 20.

Among the aluminosilicates, preference is given to those commerciallyavailable under the names zeolithe A, B, X and HS, and also to mixturescomprising two or more of those components. Zeolithe A is preferred.

Among the polycarboxylates, preference is given topolyhydroxycarboxylates, especially citrates, and acrylates and alsocopolymers thereof with maleic anhydride. Preferred poly-carboxylicacids are nitrilotriacetic acid, ethylenediaminetetraacetic acid andethylene-diamine disuccinate either in racemic form or in theenantiomerically pure (S,S) form.

As component D) especially suitable are alkali metal salts of1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonicacid), ethylenediaminetetramethylene-phosphonic acid anddiethylenetriaminepentamethylenephosphonic acid,amino-trimethylene-phosphonic acid, as well as mixtures thereof and thesalts therefrom.

As the peroxide component E) there come into consideration, for example,the organic and inorganic peroxides known in the literature andavailable commercially that bleach textile materials at conventionalwashing temperatures, for example at from 10 to 95° C.

In particular, the organic peroxides are, for example, monoperoxides orpolyperoxides having alkyl chains of at least 3, preferably 6 to 20,carbon atoms; in particular diperoxydicarboxylates having 6 to 12 Catoms, such as diperoxyperacetates, diperoxypersebacates,diperoxyphthalates and/or diperoxydodecanedioates, especially theircorresponding free acids, are of interest. It is also possible to useperoxy acid precursors in combination with H₂O₂. Especially preferredare mono- or polyperoxide, especially organic peracids or their saltssuch as phthalimidoperoxycapronic acid, peroxybenzic acid, peraceticacid, diperoxydodecandiacid, diperoxynonandiacid, diperoxydecandiacid,diperoxyphthalic acid or their salts.

The amount of peroxide in the washing, cleaning, disinfecting orbleaching agent is preferably 0.5–30 wt-%, preferably 1–20 wt-% and morepreferably 1–15 wt-%. In case a peroxide is used, the lower limit ispreferably 2 wt-%, especially 5 wt-%.

Preferably, however, inorganic peroxides are used, for examplepersulfates, perborates, percarbonates and/or persilicates. It will beunderstood that mixtures of inorganic and/or organic peroxides can alsobe used. The peroxides may be in a variety of crystalline forms and havedifferent water contents, and they may also be used together with otherinorganic or organic compounds in order to improve their storagestability.

The peroxides are added to the washing, cleaning, disinfecting orbleaching agents preferably by mixing the components, for example usinga screw metering system and/or a fluidised bed mixer.

The washing or cleaning agents may comprise, in addition to thecombination according to the invention, one or more optical brighteners,for example from the class bis-triazinylamino-stilbenedisulfonic acid,bis-triazolyl-stilbenedisulfonic acid, bis-styryl-biphenyl orbis-benzofuranylbiphenyl, a bis-benzoxalyl derivative,bis-benzimidazolyl derivative or coumarin derivative or a pyrazolinederivative.

The washing or cleaning agents used will usually contain one or moreauxiliaries such as soil suspending agents, for example sodiumcarboxymethylcellulose; salts for adjusting the pH, for example alkalior alkaline earth metal silicates; foam regulators, for example soap;salts for adjusting the spray drying and granulating properties, forexample sodium sulphate; perfumes; and also, if appropriate, antistaticand softening agents; such as smectite clays; photobleaching agents;pigments; and/or shading agents. These constituents should, of course,be stable to any bleaching system employed. Such auxiliaries can bepresent in an amount of, for example, 0.1 to 20 wt-%, preferably 0.5 to10 wt-%, especially 0.5 to 5 wt-%, based on the total weight of thewashing or cleaning agent.

Furthermore, the washing, cleaning, disinfecting or bleaching agent canoptionally contain enzymes. Enzymes can be added to washing, cleaningdisinfecting or bleaching agent for stain removal. The enzymes usuallyimprove the performance on stains that are either protein- orstarch-based, such as those caused by blood, milk, grass or fruitjuices. Preferred enzymes are cellulases, proteases, amylases andlipases. Preferred enzymes are cellulases and proteases, especiallyproteases. Cellulases are enzymes which act on cellulose and itsderivatives and hydrolyze them into glucose, cellobiose,cellooligosaccharide. Cellulases remove dirt and have the effect ofmitigating the roughness to the touch. Examples of enzymes to be usedinclude, but are by no means limited to, the following:

-   proteases as given in U.S. Pat. No. 6,242,405, column 14, lines 21    to 32;-   lipases as given in U.S. Pat. No. 6,242,405, column 14, lines 33 to    46;-   amylases as given in U.S. Pat. No. 6,242,405, column 14, lines 47 to    56; and-   cellulases as given in U.S. Pat. No. 6,242,405, column 14, lines 57    to 64.

The enzymes can optionally be present in the washing, cleaning,disinfecting or bleaching agents. When used, the enzymes are usuallypresent in an amount of 0.01–5 wt-%, preferably 0.05–5 wt-% and morepreferably 0.1–4 wt-%, based on the total weight of the washing,cleaning disinfecting or bleaching agent.

In addition to the new crystal modification of Mn(III)saltren (compound(2)) it is also possible to use further transition metal salts orcomplexes known as bleach-activating active ingredients and/orconventional bleach activators, that is to say compounds that, underperhydrolysis conditions, yield unsubstituted or substituted perbenzo-and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms,especially from 2 to 4 carbon atoms. Suitable bleach activators includethe customary bleach activators, mentioned at the beginning, that carryO— and/or N-acyl groups having the indicated number of carbon atomsand/or unsubstituted or substituted benzoyl groups. Preference is givento polyacylated alkylenediamines, especially tetraacetylethylenediamine(TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU),N,N-diacetyl-N,N-dimethylurea (DDU), acylated triazine derivatives,especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),compounds of formula (3):

wherein R₄ is a sulfonate group, a carboxylic acid group or acarboxylate group, and wherein R₅ is linear or branched (C₇–C₁₅)alkyl,especially activators known under the names SNOBS, SLOBS and DOBA,acylated polyhydric alcohols, especially triacetin, ethylene glycoldiacetate and 2,5-diacetoxy-2,5-dihydrofuran, and also acetylatedsorbitol and mannitol and acylated sugar derivatives, especiallypentaacetylglucose (PAG), sucrose polyacetate (SUPA),pentaacetylfructose, tetraacetylxylose and octaacetyllactose as well asacetylated, optionally N-alkylated glucamine and gluconolactone. It isalso possible to use the combinations of conventional bleach activatorsknown from German Patent Application DE-A-4443177. Nitrile compoundsthat form perimine acids with peroxides also come into consideration asbleach activators.

Further preferred additives to the washing or cleaning agents accordingto the invention are dye fixing agents and/or polymers which, during thewashing of textiles, prevent staining caused by dyes in the washingliquor that have been released from the textiles under the washingconditions. Such polymers are preferably polyvinylpyrrolidones,polyvinylimidazole, polyvinylpyridine-N-oxides or polybetaines which mayhave been modified by the incorporation of anionic or cationicsubstituents, especially those having a molecular weight in the range offrom 5000 to 60000, more especially from 10000 to 50000. Such polymersare usually used in an amount of from 0.01 to 5 wt-%, preferably 0.05 to5 wt-%, especially 0.1 to 2 wt-%, based on the total weight of thewashing or cleaning agent t agent. Preferred polymers are those given inWO-A-02/02865 (see especially page 1, last paragraph and page 2, firstparagraph).

The above mentioned washing or cleaning agents can take a variety ofphysical forms including powder, granular, tablet and liquid forms.Examples thereof are conventional powder heavy-duty detergents, compactand supercompact heavy-duty detergents and tablets, like heavy-dutydetergent tablets. One important physical form is the so-calledconcentrated granular form adapted to be added to a washing machine.

Of importance are also the so-called compact (or supercompact)detergents. In the field of detergent manufacture, a trend has developedrecently towards the production of compact detergents, which containincreased amounts of active substance. In order to minimize energyexpenditure during the washing process, the compact detergents arerequired to operate efficiently at temperatures as low as 40° C., oreven at room temperatures, e.g. at 25° C. Such detergents usuallycontain only low amounts of fillers or processing aids, like sodiumsulfate or sodium chloride. The amount of such fillers is usually 0–10wt-%, preferably 0–5 wt-%, especially 0–1 wt-%, based on the totalweight of the detergent agent. Such detergents usually have a bulkdensity of 650–1000 g/l, preferably 700–1000 g/l and especially 750–1000g/l.

The washing or cleaning agents can also be present in the form oftablets. Relevant characteristics of tablets are ease of dispensing andconvenience in handling. Tablets are the most compact delivery of soliddetergents and have a bulk density of, for example, 0.9 to 1.3 kg/liter.To enable fast disintegration laundry detergent tablets generallycontain special disintegrants:

-   -   Effervescents such as carbonate/hydrogencarbonate/citric acid;    -   swelling agents like cellulose, carboxymethyl cellulose,        cross-linked poly(N-vinylpyrrollidone);    -   quickly dissolving materials such as Na (K) acetate, or Na (K)        citrate;    -   rapidly dissolving water-soluble rigid coating such as dicarboxy        acids.        The tablets can also contain combinations of any of the above        disintegrants.

The washing or cleaning agents may also be formulated as an aqueousliquid comprising 5–50 wt-%, preferably 10–35 wt-% water or as anon-aqueous liquid detergent, containing not more than 5 wt-%,preferably 0–1 wt-% of water, based on the total weight of the washingor cleaning agent. Non-aqueous liquid detergent compositions can containother solvents as carriers. Low molecular weight primary or secondaryalcohols exemplified by methanol, ethanol, propanol, and isopropanol aresuitable. Monohydric alcohols are preferred for solubilizing surfactant,but polyols such as those containing from 2 to about 6 carbon atoms andfrom 2 to about 6 hydroxy groups (e.g., 1,3-propanediol, ethyleneglycol, glycerine, and 1,2-propanediol) can also be used. Thecompositions may contain from 5 to 90 wt-%, typically 10 to 50 wt-% ofsuch carriers, based on the total weight of the detergent agent. Thedetergents can also be present as the so-called “unit liquid dose” form.

The washing or cleaning agents are usually formulated that the washingliquor has pH value of about 6.5–11, preferably 7.5–11 during the wholewashing procedure. The liquor ration in the washing process is usually1:4 to 1:40, preferably 1:4 to 1:15, more preferably 1:4 to 1:10,especially preferably 1:5 to 1:9.

The washing procedure is usually done in washing machine.

There are various types of washing machines, for example:

-   -   top-loader-washing machines with a verticle rotating axis; these        machines, which have usually a capacity of about 45 to 83        liters, are used for washing processes at temperatures of        10–50° C. and washing cycles of about 10–60 minutes. Such types        of washing machines are often used in the USA;    -   front-loader-washing machines with a horizontal rotating axis;        these machines, which have usually a capacity of about 8 to 15        liters, are used for washing processes at temperatures of        30–95° C. and washing cycles of about 10–60 minutes. Such types        of washing machines are often used in Europe;    -   top-loader-washing machines with a verticle rotating axis; these        machines, which have usually a capacity of about 26 to 52        liters, are used for washing processes at temperatures of        5–25° C. and washing cycles of about 8–15 minutes. Such types of        washing machines are often used in Japan.

The washing, cleaning, disinfecting or bleaching agent according to theinvention can also be used in a soaking process, where the stainedtextiles are left for 0.5–24 hours in a solution or suspension of thedetergent and/or bleaching laundry additive without agitation. Soakingcan take place for example in a bucket or in a washing machine. Usuallythe textiles are washed and/or rinsed after the soaking process.

It is also possible that the new crystal modification of the 1:1manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) is incorporated into a granule, which comprise suitablegranulation auxiliaries. Such granules are suitable for incorporationinto a powder- or granule-form washing, cleaning, disinfecting orbleaching agent.

Surprisingly, the new crystal modification of Mn(III)saltren (compound(2)) also exhibits a markedly improved bleach-catalysing action oncoloured stains which occur on wall or floor tiles, even at lowtemperature.

The use of the new crystal modification of Mn(III)saltren (compound (2))as catalysts for reactions with peroxy compounds in cleaning solutionsfor hard surfaces, especially for wall or floor tiles, is therefore ofspecial interest.

The new crystal modification of Mn(III)saltren (compound (2)) also has,together with peroxy compounds, excellent antibacterial action. The useof the new crystal modification of Mn(III)saltren (compound (2)) forkilling bacteria or for protecting against bacterial attack is thereforelikewise of interest.

The new crystal modification of Mn(III)saltren (compound (2)) are alsooutstandingly suitable for selective oxidation in the context of organicsynthesis, especially the oxidation of organic molecules, e.g. ofolefins to form epoxides. Such selective transformation reactions arerequired especially in process chemistry. The invention accordinglyrelates also to the use of the metal complex compounds of formula (1) inselective oxidation reactions in the context of organic synthesis.

The new crystal modification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) is obtainableby

-   α) adding a solution comprising 3 parts of salicylaldehyd and 1 part    of tris-(2-aminoethyl) amine to a Mn(III) solution, which can    optionally comprise some amount of a base, such as NaOH, KOH, etc. .    . and-   β) isolation and purification of the 1:1 manganese (III) complex of    N,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)).

Suitable organic solvents for step α) are DMF, N-methylpyrrolidone,Dimethylsufoxide or alcohols such as methanol, ethanol, butanol etc. . ..

The reaction temperature for step α) are preferably between 15–50° C.,more preferably between 20–40° C., most preferably room temperature (25°C.).

The isolation and purification (step β) is done by conventional means.Preferably, the compound is filtrated, washed with some amount of thesolvent and dried in vacuum.

The present invention is illustrated but in no way limited by thefollowing examples.

EXAMPLE 1

To an ethanolic solution comprising 3 parts of salicylic aldehyde, 1part of tris-(2-aminoethyl)-amine and 2 equivalents of a NaOH-solution(50%), which has been stirred at 25° C., a stoichiometric amount of anethanolic Mn(III)salt solution is added. The Mn(III)saltren with newcrystal form is obtained after a few minutes. The precipitated compoundis filtered off, washed and dried in vacuum.

EXAMPLE 2

3 parts of salicylic aldehyde and 1 part of tris-(2-aminoethyl)amine aresolved in DMF. This solution is stirred for 20 h at a temperature of 25°C. Afterwards, the Mn(III)salt solved in DMF is added. Simultaneously, 1wt-% of a Mn(III)saltren seed crystal, obtainable according to Example 1is also added to the solution. The Mn(III)saltren with new crystal formis obtained after a few minutes. The precipitated compound is filteredoff, washed and dried in vacuum.

EXAMPLES 3–26

In Table 3a, 3b and 3c we show examples for compositions of detergentsand laundry bleaching additives, containing the Mn(III)saltren with newcrystal form (Examples 3–26)

TABLE 3a Ingredients of detergent powders and laundry bleachingadditives Ingredients A B C D Sodium laurylbenzene-sulfonate (LAS)   8%  8%   8%  10% Sodium lauryl ether sulfate (AES)   3%   3%   3%   3%Dobanol 23–6.5 (non-ionic alcoholethoxylate)   5%   5%   5%   4% ZeoliteA  22%  22%  20% — Polycarboxylate (co-builder)   5%   5%   5% — Sodiumtripolyphosphate — — —  30% Soda ash  21%  21%  21%  17% Sodium silicate  4%   4%   4%   5% Sodium sulfate   5%   5%   5%  14%Hydroxyethanediphosphonic acid (complexing agent) 0.5% 0.5% 0.5% —Cellulase 1.5% — — — Protease — 1.5% 1.5% — Carboxymethylcellulose   1%  1%   1%   2% Sodium percarbonate  15%  15%  15%  10% TAED — — 2.5% —polyvinylpyrrolidone — — — — Soap   2%   2%   2% — Fluorescent whiteningagent 0.1% 0.1% 0.1% 0.2% Perfume 0.1% 0.1% 0.1% 0.1% Granule: TheMn(III)saltren with new crystal modification X% X% X% X% PEG 8000 1.5 *X% 1.5 * X% 1.5 * X% 1.5 * X% TiO₂ 1.5 * X% 1.5 * X% 1.5 * X% 1.5 * X%CaSO₄ 3 * X% 3 * X% 3 * X% 3 * X% Maize starch 3 * X% 3 * X% 3 * X% 3 *X% In each of the above detergents a sufficient amount of water is usedto give 100%.

TABLE 3b Ingredients of detergent powders and laundry bleachingadditives Ingredients E F G H Sodium laurylbenzene-sulfonate (LAS)   8%—   5% — Sodium lauryl ether sulfate (AES)   3% —   1% — Dobanol 23–6.5(non-ionic alcoholethoxylate)   5% —   2% — Zeolite A  22% —  12% —Polycarboxylate (co-builder)   5% —   2% — Sodium tripolyphosphate — — —— Soda ash  21%  45%  11% — Sodium silicate   4% — — — Sodium sulfate  5% —   2% — Hydroxyethanediphosphonic acid (complexing agent) 0.5% — —— Cellulase — — — — Protease 1.5% —   1% — Carboxymethylcellulose   2% —0.4% — Sodium percarbonate  15%  50%  60%  95% TAED — — — —polyvinylpyrrolidone   1% — — — Soap   2% — — — Fluorescent whiteningagent 0.1% — 0.1% 0.1% Perfume 0.1% 0.1% 0.1% 0.1% Granule: TheMn(III)saltren with new crystal modification X% X% X% X% PEG 8000 1.5 *X% 1.5 * X% 1.5 * X% 1.5 * X% TiO₂ 1.5 * X% 1.5 * X% 1.5 * X% 1.5 * X%CaSO₄ 3 * X% 3 * X% 3 * X% 3 * X% Maize starch 3 * X% 3 * X% 3 * X% 3 *X% In each of the above detergents a sufficient amount of water is usedto give 100%.

In Tables 3a and 3b, the Mn(III)saltren with the new crystalmodification forms a granule together with PEG 8000, TiO₂, CaSO₄ andmaize starch.

TABLE 3c (Laundry product compositions) Amount X of the Mn(III)saltrenwith Laundry product from Examples new crystal form used (see Table 1a)table 1a 3 0.05% A 4  0.1% A 5  0.3% A 6 0.05% B 7  0.1% B 8  0.3% B 90.05% C 10  0.1% C 11  0.3% C 12 0.05% D 13  0.1% D 14  0.3% D 15 0.05%E 16  0.1% E 17  0.3% E 18 0.05% F 19  0.1% F 20  0.3% F 21 0.05% G 22 0.1% G 23  0.3% G 24 0.05% H 25  0.1% H 26  0.3% H

EXAMPLE 27

Use of The Mn(III)saltren with new crystal form as a bleaching catalystin a laundry bleaching process.

A cloth of 3 g of tea-stained cotton (BC-1, CFT, Holland) is washed in300 ml of bleach liquor. The bleach liquor contains 0.71 g of sodiumcarbonate and 0.75 g of sodium percarbonate. The water hardnesscorresponds to 50 ppm of CaCO₃. The liquor contains optionally 0.004 gof the Mn(III)saltren with new crystal form as a bleaching catalyst. TheMn(III)saltren with new crystal form is added in the form of a granule,containing 10% of the Mn(III)saltren with new crystal form and 90%formulation auxiliaries.

The bleaching is conducted in beakers in a LINITEST apparatus at 25° C.over 30 minutes. After bleaching the cloth is rinsed and ironed and thereflection spectrum measured with a SPECTRAFLASH 2000 instrument and aretransformed into brightness Y values according to the CIE standardprocedure. The bleaching effect is given as DY═Y(after washing)−Y(beforewashing).

The results obtained are set out in the following Table 4. The resultsdemonstrate the bleching effect of the Mn(III)saltren complex with newcrystal structure.

TABLE 4 Composition of bleaching liquor DY no Mn(III)saltren complex 8.80.004 g of Mn(III)saltren complex with new crystal form 13.5

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1: shows the powder X-ray diffraction pattern of Mn(III)saltren(compound (2)), obtained from Example 1. The powder sample of the newcrystal modification of Mn(III)saltren (compound (2)) has been analysedby a STOE-powder-diffractometer at room temperature (25° C.) under CuX-ray [λ(CuKα)=1.540598 Å].

FIG. 2. shows the powder X-ray diffraction pattern of Mn(III)saltren(compound (2)), obtained from Example 2. The powder sample of the newcrystal modification of Mn(III)saltren (compound (2)) has been analysedby a STOE-powder-diffractometer at room temperature (25° C.) under CuX-ray [λ(CuKα)=1.540598 Å].

1. A crystal modification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine

characterized by a peak at a d-spacing of about 6.87 Å in its powderX-ray diffraction pattern.
 2. A crystal modification of 1:1 manganese(III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound(2)) according to claim 1, characterized by a peak at d-spacing of about6.87 Å and further characterized by d spacing at about 12.69 Å in itspowder X-ray diffraction pattern.
 3. A crystal modification of 1:1manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) according to claim 2, characterized by peaks atd-spacings of about 6.87 and 12.89 Å and further characterized by peaksof about 3.51, 3.65, 4.20, 4.63, 4.95, 5.30, 6.38, 7.50, and 10.57 Å inits powder X-ray diffraction pattern.
 4. A crystal modification of the1:1 manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) according to claim 3, characterized by peaks atd-spacings of about 3.51, 3.65, 4.20, 4.63, 4.95, 5.30, 6.38, 6.87,7.50, 10.57 and 12.69 Å and further characterized by peaks of about2.22, 2.48, 2.94, 3.14, 3.76, 3.94, 5.82, 6.19, and 8.59 Å in its powderX-ray diffraction pattern.
 5. A crystal modification of 1:1 manganese(III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine (compound(2)) according to claim 4, which has a characteristic X-ray powderpattern obtained by X-ray diffraction on a powder sample of the crystalmodification in a STOE-powder-diffractometer at room temperature (25°C.) under Cu X-ray [λ(CuKα)=1.540598 Å] represented by the followingspacings between lattice planes: d(Å) Intensity 12.69 strong 10.57medium 8.59 weak 7.50 medium 6.87 strong 6.38 medium 6.19 weak 5.82 weak5.30 medium 4.95 medium 4.63 medium 4.20 medium 3.94 weak 3.76 weak 3.65medium 3.51 medium 3.14 weak 2.94 weak 2.48 weak 2.22 weak.


6. A crystal modification of 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) according toclaim 1, characterized in accordance with X-ray diffraction on itssample single crystal that it is represented by the following basiccrystallographic data: Crystal system monoclinic Space group P 2₁/n a[Å]7.906 b[Å] 25.609 c[Å] 11.736 α[°] 90 β[°] 96.55 γ[°] 90 V[Å³] 2360.6Structure unit per cell (Z) 4 Absorption coefficient μ [mm⁻¹] 0.597Crystal system monoclinic F(000)
 1064.


7. A method of catalyzing oxidation reactions comprising incorporatinginto a reaction mixture a catalytically effective amount of the crystalmodification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)) according toclaim
 1. 8. A method according to claim 7, wherein the crystalmodification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine is used in a washing,cleaning, disinfecting or bleaching agent.
 9. A method according toclaim 8, wherein the crystal modification of the 1:1 manganese (III)complex of N,N′,N″-tris[salicylideneaminoethyl]amine is used incombination with a peroxy compound for the bleaching of spots or stainson textile material or for the prevention of the redeposition ofmigrating dyes in the context of a washing process of textile materials.10. A method according to claim 8, wherein the crystal modification ofthe 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine is used as a catalyst forreactions with a peroxy compound for bleaching in the context ofpaper-making.
 11. A washing, cleaning, disinfecting or bleaching agent,containing I) 0–50% by weight, A) of at least one anionic surfactantand/or B) of at least non-ionic surfactant, II) 0–70% by weight, C) ofat least one builder substance, III) 0–10% by weight, D) of at least one(poly)phosponate and/or aminoalkylene-poly(alkylenephosphonate), IV)1–99% by weight, E) of at least one peroxide and/or of at least oneperoxide-forming substance, and V) F) the crystal modification of the1:1 manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) according to claim 1 whereby when 0.2 to 20 g/liter ofthe washing, cleaning, disinfecting and bleaching agent are added to aliquor, a concentration of 0.2–50 mg/liter of compound (2) in the liquoris provided.
 12. A process for the preparation of the modification ofthe 1:1 manganese (III) complex ofN,N′,N″-tris[salicylidene-aminoethyl]amine (compound (2)) according toclaim 1 by a) adding a solution comprising 3 parts of salicylic aldehydeand 1 part of tris-(2-aminoethyl)amine to a Mn(III) solution, which canoptionally comprise some amount of a base, and b) isolation andpurification of the 1:1 manganese (III) complex ofN,N′,N″-tris[salicylideneaminoethyl]amine (compound (2)).
 13. A washing,cleaning, disinfecting or bleaching agent according to claim 11,containing I) 0–30% by weight, A) of at least one anionic surfactantand/or B) of at least non-ionic surfactant, II) 0–50% by weight, C) ofat least one builder substance, III) 0–5% by weight, D) of at least one(poly)phosponate and/or aminoalkylene-poly(alkylenephosphonate), IV)1–70% by weight, E) of at least one peroxide and/or of at least oneperoxide-forming substance, and V) F) the crystal modification of the1:1 manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)), whereby when 0.2 to 20 g/liter of the washing, cleaning,disinfecting and bleaching agent are added to a liquor, a concentrationof 0.2–30 mg/liter of compound (2) in the liquor is provided.
 14. Amethod according to claim 8, wherein the crystal modification of the 1:1manganese (III) complex of N,N′,N″-tris[salicylideneaminoethyl]amine(compound (2)) is used in combination with a peroxy compound for thecleaning of hard surfaces.